U.S. patent application number 12/376649 was filed with the patent office on 2010-07-15 for lubricious anaerobic curable compositions.
This patent application is currently assigned to Henkel Corporation. Invention is credited to Shabbir Attarwala, Prakash S. Patel.
Application Number | 20100179078 12/376649 |
Document ID | / |
Family ID | 39082311 |
Filed Date | 2010-07-15 |
United States Patent
Application |
20100179078 |
Kind Code |
A1 |
Patel; Prakash S. ; et
al. |
July 15, 2010 |
LUBRICIOUS ANAEROBIC CURABLE COMPOSITIONS
Abstract
The present invention relates to lubricious anaerobic curable
compositions.
Inventors: |
Patel; Prakash S.;
(Algonquin, IL) ; Attarwala; Shabbir; (Simsbury,
CT) |
Correspondence
Address: |
Loctite Corporation
One Henkel Way
Rocky Hill
CT
06067
US
|
Assignee: |
Henkel Corporation
Rocky Hill
CT
|
Family ID: |
39082311 |
Appl. No.: |
12/376649 |
Filed: |
August 1, 2007 |
PCT Filed: |
August 1, 2007 |
PCT NO: |
PCT/US07/17261 |
371 Date: |
February 6, 2009 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
60822112 |
Aug 11, 2006 |
|
|
|
Current U.S.
Class: |
508/100 ;
427/384; 508/116; 508/155; 508/175; 508/178; 508/463 |
Current CPC
Class: |
C09D 131/02 20130101;
C09D 133/066 20130101; C09D 133/14 20130101 |
Class at
Publication: |
508/100 ;
508/463; 508/116; 508/178; 508/175; 508/155; 427/384 |
International
Class: |
C10M 105/34 20060101
C10M105/34; C10M 103/02 20060101 C10M103/02; C10M 103/06 20060101
C10M103/06; B05D 3/00 20060101 B05D003/00 |
Claims
1. An anaerobic curable composition having lubricity, comprising:
(a) a (meth)acrylate component; (b) an anaerobic cure-inducing
composition; and (c) a lubricious agent.
2. The composition according to claim 1, wherein the (meth)acrylate
component is represented by H.sub.2C.dbd.CGCO.sub.2R.sup.1, wherein
G is a member selected from the group consisting of H, halogen and
alkyl having from 1 to about four carbon atoms, and R.sup.1 is a
member selected from the group consisting of alkyl, cycloalkyl,
aklenyl, cycloalkenyl, alkaryl, and aryl groups having from 1 to
about 16 carbon atoms, with or without substitution or interruption
by a member selected from the group consisting of silane, silicon,
oxygen, halogen, carbonyl, hydroxyl, ester, carboxylic acid, urea,
urethane, carbamate, amine, amide, sulfur, sulonate and
sulfone.
3. The composition according to claim 1, wherein the (meth)acrylate
component is a member selected from the group consisting of
silicone(meth)acrylates, polyethylene glycol di(meth)acrylates,
bisphenol-A-(meth)acrylates, alkoxylated
bisphenol-A-(meth)acrylates, bisphenol-F-(meth)acrylates,
ethoxylated bisphenol-F-(meth)acrylates,
tetrahydrofuran(meth)acrylates and di(meth)acrylates,
hydroxypropyl(meth)acrylate, hexanediol di(meth)acrylate, and
trimethylol propane tri(meth)acrylate.
4. The composition according to claim 1, wherein the lubricious
agent is a member selected from the group consisting of graphite,
calcium oxide, calcium carbonate, calcium fluoride, calcium
stearate, magnesium oxide, magnesium carbonate, magnesium fluoride,
magnesium stearate, boron nitride, polyethylene, polypropylene and
polytetrafluoroethylene and combinations thereof.
5. Reaction products of the composition according to claim 1.
6. A process for preparing a reaction product from an anaerobic
curable composition, comprising the steps of: apply an anaerobic
curable composition according to claim 1, to a desired substrate
surface and exposing the composition to an anaerobic environment
for a time sufficient to cure the composition.
7. A method of preparing a lubricious anaerobic curable composition
in accordance with claim 1, comprising the step of: mixing
together: a (meth)acrylate component, an anaerobic cure inducing
composition and a lubricious agent.
8. A lubricious anaerobic curable composition, consisting
essentially of: (a) a (meth)acrylate component; (b) an anaerobic
cure-inducing composition; and (c) a lubricious agent; and (d)
optionally, one or more additives selected from the group
consisting of free radical initiators, free radical accelerators,
free radical inhibitors, metal catalysts, thickneners,
plasticizers, fillers, and toughening agents.
9. A composition comprising a bond formed between two mated
substrates with the composition of claim 1.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to lubricious anaerobic
curable compositions.
[0003] 2. Brief Description of Related Technology
[0004] Anaerobic adhesive compositions generally are well-known.
See e.g., R. D. Rich, "Anaerobic Adhesives" in Handbook of Adhesive
Technology, 29, 467-79, A. Pizzi and K. L. Mittal, eds., Marcel
Dekker, Inc., New York (1994), and references cited therein. Their
uses are legion and new applications continue to be developed.
[0005] Conventional anaerobic adhesives ordinarily include a
free-radically polymerizable acrylate ester monomer, together with
a peroxy initiator and an inhibitor component. Many times, such
anaerobic adhesive compositions also contain accelerator components
to increase the speed with which the composition cures.
[0006] Desirable anaerobic cure-inducing compositions to induce and
accelerate cure may include saccharin, toluidines, such as
N,N-diethyl-p-toluidine ("DE-p-T") and N,N-dimethyl-o-toluidine
("DM-o-T"), acetyl phenylhydrazine ("APH"), maleic acid, and
quinones, such as napthaquinone and anthraquinone. See e.g., U.S.
Pat. No. 3,218,305 (Krieble), U.S. Pat. No. 4,180,640 (Melody),
U.S. Pat. No. 4,287,330 (Rich) and U.S. Pat. No. 4,321,349
(Rich).
[0007] Anaerobic curable compositions are oftentimes used as thread
lockers. In such use, lubricity is desired, but conventional thread
lockers fall short, particularly in terms of clamp load.
Insufficient clamp load means that a higher torque is required for
disassembly of the nut and bolt assembly. Higher torque may go
beyond the manufactures' recommended specification.
[0008] U.S. Pat. No. 5,498,351 (Heffling) claims a process for
making anti-seize lubricant compositions, and sets forth
compositions of this type which include naphthenic oil, lubricating
grease, graphite, silicon fluid, and metal flake/oil suspension
(65% aluminum flake and 35% oil).
[0009] It would be desirable to provide anaerobic curable
compositions with lubricity to prevent seizing of threaded
fasteners.
SUMMARY OF THE INVENTION
[0010] The present invention provides anaerobic curable
compositions with lubricity. The anaerobic curable compositions are
typically used as adhesives or sealants.
[0011] The anaerobic curable compositions include (a) a
(meth)acrylate component; (b) an anaerobic cure-inducing
composition; and (c) a lubricious agent.
[0012] The addition of these materials into anaerobic curable
compositions as a replacement for some or all of the amount of
conventional anaerobic cure accelerators (such as o-benzoic
sulfimide or saccharin, used interchangeably throughout) and/or
aromatic amines (such as toluidines like diethyl-p-toluidine and
dimethyl-o-toluidine) surprisingly provides at least comparable
cure speeds and physical properties for the reaction products
formed therefrom.
[0013] This invention also provides anaerobic curable compositions
and anaerobic curable composition systems prepared with such
lubricious agents, methods of preparing and using the inventive
anaerobic curable compositions as well as reaction products of the
inventive anaerobic curable compositions.
[0014] The present invention will be more fully appreciated by a
reading of the "Detailed Description of the Invention", and the
illustrative examples which follow thereafter.
DETAILED DESCRIPTION OF THE INVENTION
[0015] The present invention provides anaerobic curable composition
having lubricity.
[0016] Anaerobic curable compositions generally are based on a
(meth)acrylate component, together with an anaerobic cure-inducing
composition. In the present invention, such anaerobic curable
compositions also include a lubricious agent to impact lubricity on
the cured reaction product. Such lubricity decreased the torque
required at a pre-determined tension.
[0017] The lubricious agent may be selected from graphite, calcium
oxide, calcium carbonate, calcium fluoride, calcium stearate,
magnesium oxide, magnesium carbonate, magnesium fluoride, magnesium
stearate, boron nitride, polyethylene, polypropylene,
polytetrafluoroethylene and combinations thereof. A particularly
desirable combination includes graphite and polyethylene.
[0018] Commercially available examples and specifications of such
lubricious agents include those from Superior Graphite under the
trade designation Graphite 5539 (particle size: 90% minimum, 20
micron, Ash: 02%, max); Mississippi Lime under the tradename QUICK
LIME (fine white powder, particle size 325 mesh or lower); Pluss
Staufer under the tradename ATOMFOR S (particle size: 99% smaller
than 325 mesh, specific gravity: 2.71); Seaforth Mineral under the
tradename FLUORSPAR SUPERFINE (specific gravity: 3.81, solubilityin
water: 16 mg/l); Witco, under the trade designation name Calicum
Stearate Regular (white powder, slightly fatty odor, melting point:
106.degree. C., specific gravity: 1.03); Kyowa Chemical under the
tradename PYROKISMA 530 IJ (white powder, MgO: 93.8, heat loss:
0.930); Dolomia Ltd under the tradename DOLOMITA #325 TB (particle
size 325 mesh); Spectrum Chemical as magnesium fluoride (particle
size: 325 mesh); CP Hall as magnesium stearate (white powder,
specific gravity: 1.028, particle size: 325 mesh); Advanced
Ceramics under the trade designation Boron Nitride HCP GRADE
(particle size: 7-10 micron, 99% passes through 325 mesh,. density:
0.4 g/cc, moisture: 0.15%); Equistar Chem under the tradename
MICROTHENE FN-510 (fine powder, particle size: 15% max, retained
270 mesh); Eastman Chemical under the tradename POLENE N-15 WAX
(white solids, specific gravity: 0.62); and Dupont under the
tradename ZONYL MP 1300 (specific gravity: 2.1-2.3).
[0019] (Meth)acrylate monomers suitable for use as the
(meth)acrylate component in the present invention may be chosen
from a wide variety of materials, such as these represented by
H.sub.2C.dbd.CGCO.sub.2R.sup.1, where G may be hydrogen, halogen or
alkyl groups having from 1 to about 4 carbon atoms, and R.sup.1 may
be selected from alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkaryl,
aralkyl or aryl groups having from 1 to about 16 carbon atoms, any
of which may be optionally substituted or interrupted as the case
may be with silane, silicon, oxygen, halogen, carbonyl, hydroxyl,
ester, carboxylic acid, urea, urethane, carbonate, amine, amide,
sulfur, sulfonate, sulfone and the like.
[0020] Additional (meth)acrylate monomers suitable for use herein
include polyfunctional (meth)acrylate monomers, such as, but not
limited to, di-or tri-functional (meth)acrylates like polyethylene
glycol di(meth)acrylates, tetrahydrofuran(meth)acrylates and
di(meth)acrylates, hydroxypropyl(meth)acrylate ("HPMA"), hexanediol
di(meth)acrylate, trimethylol propane tri(meth)acrylate ("TMPTMA"),
diethylene glycol dimethacrylate, triethylene glycol dimethacrylate
("TRIEGMA"), tetraethylene glycol dimethacrylate, dipropylene
glycol dimethacrylate, di-(pentamethylene glycol) dimethacrylate,
tetraethylene diglycol diacrylate, diglycerol tetramethacrylate,
tetramethylene dimethacrylate, ethylene dimethacrylate, neopentyl
glycol diacrylate, trimethylol propane triacrylate and bisphenol-A
mono and di(meth)acrylates, such as ethoxylated bisphenol-A
(meth)acrylate ("EBIPMA"), and bisphenol-F mono and
di(meth)acrylates, such as ethoxylated bisphenol-F
(meth)acrylate.
[0021] Still other (meth)acrylate monomers that may be used herein
include silicone(meth)acrylate moieties ("SiMA"), such as those
taught by and claimed in U.S. Pat. No. 5,605,999 (Chu), the
disclosure of which is hereby expressly incorporated herein by
reference.
[0022] Of course, combinations of these (meth)acrylate monomers may
also be used.
[0023] The (meth)acrylate component should comprise from about 10
to about 90 percent by weight of the composition, such as about 60
to about 90 percent by weight, based on the total weight of the
composition.
[0024] Recently, additional components have been included in
traditional anaerobic curable compositions to alter the physical
properties of either the curable compositions or the reaction
products thereof.
[0025] For instance, one or more of maleimide components, thermal
resistance-conferring coreactants, diluent components reactive at
elevated temperature conditions, mono- or poly-hydroxyalkanes,
polymeric plasticizers, and chelators (see International Patent
Application No. PCT/US98/13704, the disclosure of which is hereby
expressly incorporated herein by reference) may be included to
modify the physical property and/or cure profile of the formulation
and/or the strength or temperature resistance of the cured
adhesive.
[0026] When used, the maleimide, coreactant, reactive diluent,
plasticizer, and/or mono- or poly-hydroxyalkanes, may be present in
an amount within the range of about 1 percent to about 30 percent
by weight, based on the total weight of the composition.
[0027] The inventive compositions may also include other
conventional components, such as free radical initiators, other
free radical co-accelerators, inhibitors of free radical
generation, as well as metal catalysts, such as iron and
copper.
[0028] A number of well-known initiators of free radical
polymerization are typically incorporated into the inventive
compositions including, without limitation, hydroperoxides, such as
CHP, para-menthane hydroperoxide, t-butyl hydroperoxide ("TBH") and
t-butyl perbenzoate. Other peroxides include benzoyl peroxide,
dibenzoyl peroxide, 1,3-bis(t-butylperoxyisopropyl)benzene,
diacetyl peroxide, butyl 4,4-bis(t-butylperoxy)valerate,
p-chlorobenzoyl peroxide, cumene hydroperoxide, t-butyl cumyl
peroxide, t-butyl perbenzoate, di-t-butyl peroxide, dicumyl
peroxide, 2,5-dimethyl-2,5-di-t-butylperoxyhexane,
2,5-dimethyl-2,5-di-t-butyl-peroxyhex-3-yne,
4-methyl-2,2-di-t-butylperoxypentane and combinations thereof.
[0029] Such peroxide compounds are typically employed in the
present invention in the range of from about 0.1 to about 10
percent by weight, based on the total weight of the composition,
with about 1 to about 5 percent by weight being desirable.
[0030] Conventional accelerators of free radical polymerization may
also be used in conjunction with the inventive anaerobic cure
accelerators. Such co-accelerators are typically of the hydrazine
variety (e.g., APH), as disclosed in the '330 and '349 patents.
[0031] Stabilizers and inhibitors (such as phenols including
hydroquinone and quinones) may also be employed to control and
prevent premature peroxide decomposition and polymerization of the
composition of the present invention, as well as chelating agents
[such as the tetrasodium salt of ethylenediamine tetraacetic acid
("EDTA")] to trap trace amounts of metal contaminants therefrom.
When used, chelators may ordinarily be present in the compositions
in an amount from about 0.001 percent by weight to about 0.1
percent by weight, based on the total weight of the
composition.
[0032] Anaerobic cure accelerators may be used in amounts of about
0.1 to about 5 percent by weight, such as about 1 to about 2
percent by weight, based on the total weight of the composition.
When used in combination with conventional accelerators (though at
lower levels, for such conventional accelerators), the inventive
accelerators should be used in amounts of about 0.01 to about 5
percent by weight, such as about 0.02 to about 2 percent by
weight.
[0033] Metal catalyst solutions or pre-mixes thereof are used in
amounts of about 0.03 to about 0.1 percent by weight. Other agents
such as thickeners, non-reactive plasticizers, fillers, toughening
components (such as elastomers and rubbers), and other well-known
additives may be incorporated therein where the art-skilled
believes it would be desirable to do so.
[0034] The present invention also provides methods of preparing and
using the inventive anaerobic adhesive compositions, as well as
reaction products of the compositions.
[0035] The compositions of the present invention may be prepared
using conventional methods which are well known to those persons of
skill in the art. For instance, the components of the inventive
compositions may be mixed together in any convenient order
consistent with the roles and functions the components are to
perform in the compositions. Conventional mixing techniques using
known apparatus may be employed.
[0036] The compositions of this invention may be applied to a
variety of substrates to perform with the desired benefits and
advantages described herein. For instance, appropriate substrates
may be constructed from steel, brass, copper, aluminum, zinc, glass
and other metals and alloys, ceramics and thermosets. The
compositions of this invention demonstrate particularly good bond
strength on steel, glass and aluminum. An appropriate primer may be
applied to a surface of the chosen substrate to enhance cure
rate.
[0037] In addition, this invention provides a method of preparing
an anaerobic curable composition, a step of which includes mixing
together a (meth)acrylate component, and an anaerobic cure-inducing
composition and a lubricious agent.
[0038] The invention also provides a process for preparing a
reaction product from the anaerobic adhesive composition of the
present invention, the steps of which include applying the
composition to a desired substrate surface and exposing the
composition to an anaerobic environment for a time sufficient to
cure the composition.
[0039] In view of the above description of the present invention,
it is clear that a wide range of practical opportunities is
provided. The following examples are provided for illustrative
purposes only, and are not to be construed so as to limit in any
way the teaching herein.
Examples
Adhesive Formulations
[0040] Generally, lubricious anaerobic curable compositions in
accordance with this invention may be prepared with these
representative components in the by weight ranges noted in Table 1.
Of course, various alternative materials may be substituted for or
included in addition to those listed below, examples of which are
given throughout the application.
TABLE-US-00001 TABLE 1 Polyethylene Glycol Dimethacrylate -- 40-80
Bisphenol A Fumarate -- 10-40 Napthoquinone -- 0.01-0.1 Tetrasodium
Ethylenediamine Tetraacetate -- 0.01-0.1 Saccharin -- 0.5-2.0
Diethyl p Toluidine -- 0.2-1.0 Dimethyl o Toluidine -- 0.2-1.0
Peroxide -- 0.2-10 Hydroxy Propyl Methacrylate -- 2-10 Synthetic
Graphite -- 5-30 Polyethylene powder -- 5-30
[0041] More specifically, Sample No. 1 as set forth in Table 2 was
prepared from the noted components in the listed amounts, by mixing
with a mechanical stirrer in glass vials.
TABLE-US-00002 TABLE 2 COMPONENTS Type Identity Amt./wt %
(Meth)acrylate Polyethylene Glycol 48.17 Dimethacrylate
Propoxylated Bisphenol A 35.15 Fumarate Chelater NaEDTA 0.04
Toluidines DE-p-T 0.46 DM-o-T 0.23 Peroxide CHP 1.75 Accelerator
Saccharin 1.346 Lubricious Graphite* 7.00 Agent Polyethylene** 5.00
*Commercially available from Superior Graphite Co., Chicago, IL, as
5539 graphite **Commercially available from Equistar Chemicals Co.,
Houston, TX, under the tradename MICROTHENE Fn 510
[0042] Sample No. 2 as set forth in Table 3 was prepared as a
control from the noted components in the listed amounts, also by
mixing with a mechanical stirrer in glass vials.
TABLE-US-00003 TABLE 3 COMPONENTS Type Identity Amt./wt %
(Meth)acrylate Polyethylene Glycol 53.30 Dimethacrylate
Propoxylated Bisphenol A 39.93 Fumarate Dye Red 0.06 Fluorescent
0.0002 Chelater NaEDTA 0.04 Toluidines DE-p-T 0.53 DM-o-T 0.27
Peroxide CHP 1.99 Accelerator Saccharin 1.53
Physical Properties
[0043] Initially, we determined the compressive shear strength for
anaerobic curable compositions using degreased steel pins and
collars. The results for Sample Nos. 1 and 2 are set forth below in
Table 4.
TABLE-US-00004 TABLE 4 Shear Strength (N/mm.sup.2) Sample No. 1
Hour 24 Hours 1 7.2 18.9 2 5.7 11.7
[0044] Next, we considered lubricity and k factor in the
determination of the amount of applied torque at predetermined bolt
tensions for anaerobic curable compositions. The nuts and bolts
used in this evaluation were constructed of 3/8''16 phosphate
steel, and were as received, and thus oily on the surface. Table 5
sets forth the data obtained with respect to the control
composition and Table 6 sets forth the data obtained with respect
to an inventive composition.
TABLE-US-00005 TABLE 5 TORQUE DETERMINATION @ SPECIFIED TENSION
LUBRICITY & K-FACTOR Bolt Tension (lbs.): 5000 Bolt Tension
(lbs.): 6000 Applied Torque Applied Torque (in.-lbs.) K Factor
(in.-lbs.) K Factor 546 0.29 659 0.29 559 0.30 656 0.29 540 0.29
619 0.28 552 0.29 670 0.30 580 0.31 692 0.31 Average: 555 0.30
Average: 659 0.29
TABLE-US-00006 TABLE 6 TORQUE DETERMINATION @ SPECIFIED TENSION
LUBRICITY & K-FACTOR Bolt Tension (lbs.): 5000 Bolt Tension
(lbs.): 6000 Applied Torque Applied Torque (in.-lbs.) K Factor
(in.-lbs.) K Factor 400 0.21 469 0.21 449 0.24 412 0.18 391 0.21
437 0.19 317 0.17 367 0.16 416 0.22 490 0.22 Average: 395 0.21
Average: 435 0.19
[0045] The lubricious anaerobic composition (Sample No. 1) shows
higher lubricity (in terms of a lower K factor) than the control
anaerobic composition (Sample No. 2) at each of 5000 lbs. and 6000
lbs. tension. This allows the assembly to achieve higher clamping
loads at lower installation torques.
* * * * *